CN1143404C - 锂二次电池 - Google Patents

锂二次电池 Download PDF

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CN1143404C
CN1143404C CNB971910294A CN97191029A CN1143404C CN 1143404 C CN1143404 C CN 1143404C CN B971910294 A CNB971910294 A CN B971910294A CN 97191029 A CN97191029 A CN 97191029A CN 1143404 C CN1143404 C CN 1143404C
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lithium
secondary battery
lithium secondary
active material
battery
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CN1198843A (zh
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山崎慎司
智
西野敬智
浅田朗
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Maxell Holdings Ltd
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Abstract

一种锂二次电池，它包括：把钛酸锂作为活性物质而包含的正极；把原料碳作为活性物质而包含的负极；以及把锂盐溶解在有机溶剂中而形成的电解液。钛酸锂最好具有用一般式：LixTiyO4(式中，0.8≤x≤1.4、1.6≤y≤2.2)表示的组成。该锂二次电池的标称电压为1.5伏，该电池具有适合作为手表用电池等大容量及优异的充放电周期特性。

Description

锂二次电池
技术领域
本发明涉及锂二次电池，更详细地说，特别涉及适合作为钟表用备份电源、小型钟及计时器等携带装置用电源、存储器备份电源等的锂二次电池。
背景技术
迄今，作为锂二次电池，主要开发的是在负极上使用金属锂及锂合金的电池。但是，在负极上使用金属锂及锂合金的情况下，当充电时，在电解液中的锂离子作为锂金属在负极上析出时，通过所析出的锂金属微细化的产生、或者通过在负极表面上的锂树枝状晶体的成长，产生内部短路，减短了电池充放电周期的寿命。因此，研究在负极上不使用金属锂及锂合金的高能量密度的锂电池。
作为手表用电源，当前使用氧化银电池等一次电池。在一次电池中，存在着把使用完了的电池销毁时所伴随的问题。因此，开发装有发电装置、不需要电池更换的手表，作为用于这种手表上的电源，使用电偶层电容器。但是，因为电偶层电容器单位体积的容量小，所以，要求代替它的电源。
发明内容
本发明的目的在于提供可以充放电、不产生销毁时所伴随的问题、大容量、且适合作为手表用电源等的锂二次电池。
即，本发明提供锂二次电池，它包括：把钛酸锂作为活性物质而包含的正极；把原料碳作为活性物质而包含的负极；以及把锂盐溶解在有机溶剂中而形成的电解液。其中，钛酸锂具有用下列一般式表示的组成：
LixTiyO4
式中，x及y分别为0.8≤x≤1.4、1.6≤y≤2.2范围内的某一个数。
通过把钛酸锂作为正极活性物质、把原料碳作为负极活性物质组合起来使用，得到标称电压为1.5伏、容易进行锂离子搀入及排出、大容量且充放电周期特性优异的锂二次电池。
附图说明
图1为示出本发明锂二次电池的一例的剖面图；
图2为示出实施例1～2的电池及比较例1的电池第1次放电时放电特性的曲线图；
图3为示出实施例1～2的电池及比较例1的电池充放电周期特性的曲线图。
具体实施方式
在本发明中，作为正极活性物质的钛酸锂，例如，通过在760～1100℃的温度下把氧化钛及锂化物加热而获得。
钛酸锂通常用一段式(I)来表示：
      LixTiyO4                 (I)
通常，式中的x及y分别为0.8≤x≤1.4、1.6≤y≤2.2范围内的某一个数。特别是，x＝1.33及y＝1.67时的钛酸锂(I)令人满意。
作为上述氧化钛，使用脱钛矿型或金红石型任一种都可以。作为锂化物可以使用例如氢氧化锂、碳酸锂、氧化锂等。
最好是把钛酸锂、导电辅助材料和粘结剂混合起来配制成正极混合剂，把正极混合剂加压成形来制作正极。
作为导电辅助材料可以使用例如鳞状石墨、乙炔黑、碳黑等。作为粘结剂，适于使用含氟树脂，作为其具体例，可以举出例如聚四氟乙烯、聚偏二氟乙烯等。
构成正极的各种成分的比例最好是作为正极活性物质的钛酸锂为70～90(重量)％，导电辅助材料为5～20(重量)％，粘结剂为1～10(重量)％。
钛酸锂的比例比上述下限小时，容量减小，有可能达不到大容量化；钛酸锂的比例比上述上限大时，由于与此相伴随的导电辅助材料及粘结剂的减少，有可能使正极混合剂的导电性及强度降低。
导电辅助材料的比例比上述下限小时，有可能使导电性降低；导电辅助材料的比例比上述上限大时，由于正极活性物质钛酸锂的减小，有可能使容量减小。
粘结剂的比例比上述下限小时，正极混合剂的粘结性降低，有可能难于成形；粘结剂的比例比上述上限大时，由于正极活性物质钛酸锂的减少，有可能使容量减小。
再者，正极的制作方法并不局限于上述例示；还有，其成分的组成也不局限于上述例示。
例如，把作为负极活性物质的原料碳、粘结剂混合起来配制成负极混合剂，把负极混合剂加压成形来制作负极。
作为负极活性物质的原料碳例如可以使用人造石墨、天然石墨、低结晶性碳、焦碳、无烟煤等，但是，特别是最好是使用人造石墨，因与其它原料碳相比，可以期待人造石墨提供大容量。
作为粘结剂，适于使用含氟树脂，作为其具体例，可以举出例如聚四氟乙烯、聚偏二氟乙烯等。
构成该负极的各种成分的比例，最好是，负极活性物质的原料碳为80～95(重量)％，粘结剂为5～20(重量)％。
作为负极活性物质的原料碳的比例比上述下限小时，有可能难于得到大容量的锂二次电池；原料碳的比例比上述上限大时，由于与此相伴随的粘结剂的减小，使粘结性降低，有可能难于成形。
再者，负极的制作方法并不局限于上述例示；还有，其构成成分也不局限于上述例示，例如，也可以在上述负极混合剂中配合导电辅助材料等。
在本发明中，作为电解液，可以使用通过把锂盐溶解在有机溶剂中而配制成有机溶剂系列的电解液。可以作为电解液溶剂使用的有机溶剂，例如有：丙撑碳酸酯、乙烯碳酸酯、丁烯碳酸酯、γ-丁内酯、1，2-二甲氧基乙烷、1，2-二甲氧基甲烷、氧杂环戊烷、二氧戊环等。
作为锂盐可以举出例如LiN(CF3SO2)2、LiClO4、LiPF6、LiBF4、LiAsF6、LiSbF6、LiCF3SO3、LiCF3CO2、LiCnF2n+1SO3(n≥2)、LiN(CF3CF2SO2)2等。尤其是，LiN(CF3SO2)2、LiPF6、LiCF3SO3、LiBF4，因其传导率高、热稳定，特别适于使用。
锂盐在电解液中的浓度并不特别限定，但其浓度通常为0.1～2mol/l特别是，最好为0.4～1.4mol/l左右。
除了作为正极、负极及电解液使用上述材料之外，锂二次电池的结构及制作方法可以与现有的锂二次电池的结构及制作方法相同。
实施例
其次，举出实施例更具体地说明本发明。但是，本发明并不通过这些实施例而限定。
实施例1
把2摩尔脱钛矿型氧化钛与1摩尔氢氧化锂混合，在空气气氛中、800℃的温度下、在电炉中经8个小时烧制，合成钛酸锂。通过原子吸光分析法进行元素分析的结果表明，可得到的钛酸锂的组成为Li1.33Ti1.67O4。
把所得到的钛酸锂(Li1.33Ti1.67O4)按重量100份、作为导电辅助材料的碳黑按重量5份及石墨按重量5份、作为粘结剂的聚四氟乙烯按重量5份，在异丙醇中混合，配制成正极混合剂，在溶剂蒸发以后，把正极混合剂成形为直径6.0mm、厚度0.5mm的圆片，通过在远红外线干燥机中、在250℃下、对这些圆片进行30分钟的干燥、脱水处理，制作成正极。
另外，把人造石墨按重量90份、作为粘结剂的聚偏二氟乙烯按重量10份，在N-甲基吡咯烷酮(N-メチルピロリドン)中混合，配制成负极混合剂，在溶剂蒸发以后，把负极混合剂成形为直径3.5mm、厚度1.0mm的圆片，通过在远红外线干燥机中、在120℃下、对这些圆片进行30分钟的干燥、脱水处理，制作成负极。
作为电解液，使用了把LiN(CF3SO2)2以1.0mol/L溶解在体积比为1∶1的乙烯碳酸酯与二乙基碳酸酯的混合溶剂中的电解流。
利用上述正极、负极及电解液，制作成具有图1所示结构的、外径6.7mm、高度2.1mm的锂二次电池。
图1中，如上所述，正极1把钛酸锂(Li1.33Ti1.67O4)作为活性物质，并包括正极混合剂的加压成形体，该正极混合剂包含：该钛酸锂；作为导电辅助材料的碳黑及石墨；作为粘结剂的聚四氟乙烯。
负极2把人造石墨作为活性物质，并包括负极混合剂的加压成形体，该负极混合剂包含：该人造石墨、作为粘结剂的聚偏二氟乙烯；把由聚丙烯制的非织造布构成的隔板3配置在正极1与负极2之间。
在电池装配时，把相当于正极1的电容量80％的金属锂配置成与该隔板3对置，当使用时，由于电解液的存在，使锂离子搀入上述负极2。
把正极1、负极2、隔板3及电解液封入到由不锈钢制的正极罐4、不锈钢制的负极罐5、聚丙烯制的绝缘垫材6形式的空间内。
实施例2
除了使用了把LiPF6代替LiN(CF3SO2)2以1.0mol/l溶解在体积比为1∶1的乙烯碳酸酯与二乙基碳酸酯的混合溶剂中而构成的电解液之外，与实施例1同样地制作锂二次电池。
比较例1
除了作为正极活性物质，使用了锂铁氧化物(LiFe5O8)代替钛酸锂之外，与实施例1同样地制作锂二次电池。
使利用上述实施例1～2及比较例1制作的电池在下列条件下进行充放电，研究第1次放电时的放电特性及充放电周期特性。
充电条件：恒定电流0.1mA，充电断开电压2.4V；
放电条件：恒定电流0.1mA，放电断开电压0.4V。
图2示出第1次放电时的放电特性，图3示出充放电周期特性。
如图2所示，与比较例1的电池相比，实施例1～2的电池在1.5V附近电池电压的平坦性高，一直到到达0.4V时，电池的容量大，是大容量的。
还有，如图3所示，与比较例1的电池相比，在同一周期次数下相比时，实施例1～2的电池的电池容量大；而且，伴随着周期次数的增加，电池容量的减小变小，充放电周期特性优异。
与此相反，比较例1的电池的电池容量小，还有，在周期初期，电池容量急剧减小，充放电周期特性差，可以认为，这些是由于，作为正极活性物质使用的锂铁氧化物在充放电时其结晶结构不稳定。
还有，除了具有上述实施例中所示的Li1.33Ti1.67O4组成式的钛酸锂之外，有关以LiTi2O4及Li0.8Ti2.2O4表示的钛酸锂，使用分别与实施例1及实施例2中使用的电解液相同组成的电解液及负极，制作与实施例1～2相同的锂二次电池，也研究其电池容量及充放电周期特性。分别得到了与实施例1～2相同的结果。
如上所说明的那样，在本发明中，通过作为正极活性物质使用以一般式LixTiyO4表示的钛酸锂、作为负极活性物质使用人造石墨等原料碳，能够提供标称电压为1.5伏、大容量、且充放电周期特性优异的锂二次电池。

Claims (4)

1.一种锂二次电池，其特征在于，包括：把钛酸锂作为活性物质而包含的正极；把原料碳作为活性物质而包含的负极；以及把锂盐溶解在有机溶剂中而形成的电解液；
其中，钛酸锂具有用下列一般式表示的组成：
LixTiyO4
式中，x及y分别为0.8≤x≤1.4、1.6≤y≤2.2范围内的某一个数。
2.根据权利要求1中所述的锂二次电池，其特征在于，一般式中的x及y分别为1.33及1.67。
3.根据权利要求1中所述的锂二次电池，其特征在于，正极的各种材料的比例为，钛酸锂为70～90重量％，导电辅助材料为5～20重量％，粘结剂为1～10重量％。
4.根据权利要求1中所述的锂二次电池，其特征在于，锂盐为从由LiN(CF3SO2)2、LiPF6、LiCF3SO3及LiBF4构成的组中选择的至少1种锂盐。
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